Polyfluorinated products



United States Patent 3,012,069 POLYFLUORINATED PRODUCTS John J. Drysdale, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware N0 Drawing. Filed June 19, 1959, Ser. No. 825,631 13 Claims. (Cl. 260-487) This invention relates to a new process for the preparation of polyfluorinated acyloin esters and polyfluorinated enediol esters, and to certain new such esters. It also includes methods of converting these esters to polyfiuorinated acyloins, 1,2-glycols, and 1,2-diketones, and to certain such new polyfluorinated products.

In my copending application Serial No. 742,037, filed June 16, 1958, now Patent No. 2,957,031, the reaction at temperatures from 100200 C. between polyfiuoroacyl halides and nickel carbonyl with aromatic compounds containing at least one hydrogen on nuclear carbon is shown to result in the formation of fiuoroalkyl aromatic compounds wherein the polyfluorocarbyl radi cal of the polyfluoroacyl halide is attached to the said hydrogen-bearing nuclear carbon atom. In my copending application Serial No. 742,062, filed June 16, 1958, now Patent No. 2,925,446, the reaction between polyfluoroacylhalides and nickel carbonyl at temperatures from 40200 C. in the absence of any other reactant or any reaction medium is shown to result in the formation of polyfiuoroolefins and polyfluoroketones.

-It has now surprisingly been discovered that the same polyfiuoroacyl halides react with nickel carbonyl in the presence of benzonitrile and at temperatures below 40 C. to form polyfiuoroacyloin esters and enediol diesters. The reaction can be schematically represented as follows:

OCOR RCOO OCOR Ni(OO) I nitrile wherein R is a monovalent perfiuorocarbyl or w-hydroor w-chloroperfluorocarbyl radical free of aliphatic unsaturation and of from three through fourteen carbons. Because of somewhat readier availability of the necessary intermediates and somewhat more convenient preparation of the products, the preferred such radicals are those of from three through ten carbons, particularly the whydro such radicals.

The operating conditions for this surprising reaction are quite critical and extremely specific. Thus, the reaction must be carried out using benzonitrile as a reaction medium. Furthermore, only nickel carbonyl and no other metal carbonyl can be used. Finally, the reaction must be effected at temperatures no higher than 40 C. and, practically speaking, in the extremely narrow temperature range from substantially room temperature to 40 C. With the shorter chain, lower boiling, more reactive perfiuoro-, w-hydroperfluoro-, and w-chloroperfluorocarbacyl halides, the reaction can be effected at somewhat lower temperatures or else in the above indicated temperature range operating under slight pressure to maintain the low boiling acyl halides in the liquid phase. However, under such conditions the operating pressure must be controlled quite narrowly so as to permit the escape from the reaction zone of the necessarily formed carbon monoxide gas. Otherwise with build-up in carbon monoxide pressure, the necessary decomposition of nickel carbonyl would be halted.

These polyfluoroacyloin esters and enediol diesters are versatile chemical intermediates. Thus, by simple alcoholysis, both the acyloin esters and the enediol diesters 3,012,059 Patented Dec. 5, 1961 can be directly converted to the corresponding acyloins according to the following reaction mechanisms:

0 COR I alcoholysis I RCOCHR RCOCHR RG00 OCOR OH I alcoholysis I RC=CR ---)RCOCHR wherein the R radicals are as previously defined. Furthermore, the acyloin esters, enediol diesters, and acyloins can be easily reduced to the corresponding polyfluorocarbyl-1,2-glycols according to the following mechanisms:

0 (JOB HO OH I reduction I RCOOHR RCHCHR I oxidation RCOCHR- RCOCOR wherein the R radicals are as previously defined. The polyfiuorosubstituted 1,2-diketones can also be prepared directly by pyrolysis of the polyfluorosubstituted enediol diesters:

R C O O O C O R I pyrolysis RC=CR RCOCOR where the Rs are as before.

The ready and direct conversion of the polyfluoroacyloin esters and polyfiuoroenediol diesters (formed from the polyfiuoroacyl halides and nickel carbonyl under the extremely specific reaction conditions just defined) to acyloins and 1,2-diketones has fundamental technical significance, in that previous attempts to prepare polyfiuorosubstituted acyloins and 1,2-diketones have failed. Thus, Haszeldine, Nature 168, 1028 (1951), and McBee et al., J. Am. Chem. Soc. 75, 4091 (1953), show that the reaction of sodium on ethyl trifiuoroacetate forms trifiuoroacetoacetic ester and trifiuoroethanol, and not the expected acyloin, CF CHOHCOCF or 1,2-diketone, CF COCOCF From these teachings, ignoring the possible significance of the different properties and frequent instability resident in first members of series, one would certainly not except such polyfluorinated acyloins or 1,2- diketones to be formed at all or, if formable, to be formed under such extremely easy conditions.

The following examples, in which the parts given are by weight unless otherwise indicated, are submitted tov illustrate further the present invention but in no way to limit it.

Example I 3 F, 66.4%; M.W., 920. Found: C, 25.7%; H, 0.6%; F, 66.2%; M.W., 900, 940.

The nuclear magnetic resonance spectrum of the enediol diester exhibited five peaks in the CF region: a doublet and four singlets in the ratio 4:424:212. This is the expected spectrum for the 1,10-dihydroperfiuoro-5- decene-5,6-diol di-5-hydroperfluorooctavalerate. The infrared spectrum showed carbonyl absorption at 5.50 microns.

Example 11 A mixture of 20 parts of benzonitrile, 1,065 parts of SH-octafluorovaleryl chloride, and 160 par-ts of nickel carbonyl was stirred at 25 C. for 24 hours under anhydrous conditions. An additional 100 parts of hemenitrile was added, and the stirring was continued at room temperature for an additional two days. At this point, 100 additional parts of nickel carbonyl was added, and stirring at room temperature was continued for an additional 14 days. Unreacted nickel carbonyl and by-product nickel chloride were then removed by filtration. Upon distillation of the filtrate there was obtained 25 parts (5% conversion) of the polyfluoroacyloin ester 1H,6H, 1OH-hexadecafiuoro-5-oxo-6-decyl SH-oct-afluorovalerate as a clear, colorless liquid boiling at 117 C. under a pressure corresponding to 3-4 mm. of mercury.

Analysis.Calcd. for C I-1 1 C, 26.2%; H, 0.6%; F, 66.4%. Found; C, 27.4%; H, 1.2%; F, 64.6%.

The nuclear magnetic resonance spectrum showed the expected (fluorine peaks in the CF region for the trihydrohexadecafiuorooxodecyl hydrooctafiuorovalerate. Continued distillation of the filtrate afiorded 181 parts (19.6% of theory) of the enediol diester 1H,10H-hexadecafiuoro-S-decene-5,6-diol di(H-octafluorovalerate) of Example I as a clear, colorless liquid boiling at 124-129 C. under a pressure corresponding to 3-4 mm. of mercury; 11 1.3255.

Example III A mixture of 115 parts of perfluorobutyryl chloride, 41 parts of nickel carbonyl, and 300 parts of benzonitrile was stirred for 72 hours at 25 C. under anhydrous conditions. The reaction mixture was filtered, and the filtrate was distilled. There was thus obtained six parts (6% of theory) of the polyfluorinated acyloin ester 5H- tetradecafluoro-4-oxo-5-octyl perfiuorobutyrate as a clear, colorless liquid boiling at 64 C. under a pressure corresponding to 18 mm. of mercury.

Analysis.Calcd. for C F O H: C, 24.3%; H, 0.2%; F, 67.3%. Found: C, 24.6%; H, 0.2%; F, 67.5%.

' The nuclear magnetic resonance spectrum showed peaks corresponding to two different types of perfluoropropyl groups in a ratio of 2:1. Proton nuclear magnetic resonance analysis showed a single saturated proton. On continued distillation there was also obtained five par-ts (5.1% of theory) of the enediol diester perfluoro-4-octene-4,5-diol di(perfluorobutyrate), i.e., 4,5- perfiuoro-4-octenylene bis(per-fluorobutyrate), as a clear, colorless liquid boiling at 89 C. under a pressure corresponding to 18mm. of mercury.

' of C F groups of equal intensity.

Example IV A mixture of 400 parts of benzonitrile, 160 parts of nickel carbonyl, and 1,055 parts of perfiuorobutyryl chloride was stirred under anhydrous conditions at room temperature for 72 hours. An additional 100 parts of nickel carbonyl-was then added, and the mixture was stirred for an additional 48 hours under the same conditions. Another 100-part portion of nickel carbonyl was then added, and stirring was continued under the same conditions for seven more days. The reaction mixture was then filtered to remove unreacted nickel carbonyl and lay-product nickel chloride. Upon distillation of the resultant filtrate, there was obtained 455 parts (51% conversion) of the enedioldiester perfluoro-4-octene-4,5- diol -di(perfluorobutyrate) as a clear, colorless liquid boiling at 89 C. under a pressure corresponding to 18 mm. of mercury, which was identical with the second product of Example II I.

Example V A mixture of 100 parts of perfiuoroglutaryl chloride, 62 parts of nickel carbonyl, and 20 parts of benzonitrile was allowed to stand with stirring at room temperature under anhydrous conditions for three days. During the course of the reaction carbon monoxide was slowly evolved, and a precipitate of nickel chloride was formed. The reaction mixture was filtered, and the nickel chloride precipitate was washed with diethyl ether. The ether Example VI A mixture of 73 parts of methanol and 600 parts of the enediol diester perfiuoro 4 octene 4,5-diol di(perfluorobutyrate)see Examples HI and IV-was stirred at 25 C. As solution took place an exothermic reaction occurred which heated the reaction mixture to reflux temperature. Upon distillation of the reaction product, there was obtained 270 parts of a mixture of methanol and methyl perfiuorobutyrate boiling at less than 70 C. under a pressure corresponding to 90 mm. of mercury and 272 parts (90% of theory) of the poly-fluoroacyloin SH-tetradecafluoro-S-hydroxy 4 octanone as a clear, colorless liquid boiling at 70-72" C. under a pressure correspond ing to 90 mm. of mercury; 22 1.4940. Infrared analysis showed carbonyl absonption at 5.67 microns and hydroxyl absorption at 2.80 microns.

'Analysis.-Calcd. for C F H O F, 67.2%. F, 66.8%.

Found Example VII Example VIII A mixture of 232 parts of perfluorobutyryl chloride, 264 parts of SH-octafluorovaleroyl chloride, parts of nickel carbonyl, and 100 parts of benzonitri'le was stirred at room temperature for 72 hours under anhydrous conditions. An additional 70 parts of nickel carbonyl was then added, and stirring was continued for an additional week. The reaction mixture was filtered, and the'filter cake was washed with diethyl ether. The ether wash was concentrated, and the ether concentrate and filtrate were Infrared combined and distilled. The liquid product, boiling at 93 C. under a pressure corresponding to 24 mm. of mercury, was stirred with excess methanol for 15 minutes. Upon distillation of the resultant reaction mixture there was obtained the polyfiuoroacyloins: (a) SH-tetradecafiuoro-5-hydroxy-4-octanonesee Example VI-boiling at 70-72 C. under a pressure corresponding to 90 mm. of mercury; (b) 1H,6H,l0H-hexadecafluoro 6 hydroxy-S- decanone-see Example VII-boiling at 74-76 C. under a pressure corresponding to 50 mm. of mercury; and (c) 50 parts of a mixture of 1H,SH-pentadecafluoro-S-hydroxy-4-nonanone and 4H,9H-pentadecafiuoro-4-hydroxy- S-nonanone as a clear, colorless liquid boiling at 87 C. under a pressure corresponding to 40 mm. of mercury. Infrared analysis showed carbonyl absorption and hydroxyl absorption. It was not possible to separate the isomers of fraction by distillation.

Analysis.-Calcd. for C H F O C, 25.2%; H, 0.8%; F, 66.6%. Found: C, 25.7%; H, 1.0%; F, 66.1%.

Example IX sponding to about mm. of mercury and 7.5 parts of the enediol perfluoro-4-octene-4,5-diol diperfluorobutyrate see Example Ill-was dropped into the heated reaction zone over a period of five minutes. The resultant pyrolysis product (collected in both traps) was combined and distilled from phosphorus pentoxide through a Spinning band column of the type described in U.S. Patent 2,712,- 520. There was thus obtained a total of 0.9 part of products boiling at 9295 C. Nuclear magnetic resonance spectra and gas chromatographic analyses indicated that the fraction, 0.45 part, boiling at 95 C. at atmospheric pressure was 90-95% pure perfluor0-4,5-octanedione, with the major impurity being the shorter chain monoketone perfluoro-4-heptanone. Infrared analysis showed strong carbonyl absorption at 5.65 microns. Approximately one third of the 95% pure product was further purified by gas chromatography for elemental anal- YSlS.

Analysis.--Calcd. for CgF O F, 67.5%. F, 67.4%.

The per-fiuoro-4,5-octanedione was further characterized by conversion to 2,3-bis(perfluoropropyl)quinoxaline. Thus, 0.25 part of o-phenylenediamine was added to 0.88 part of the above perfiuoro-4,5-octanedione. A vigorous reaction ensued. The resultant liquid product was heated with 5.4 parts of acetic anhydride for one hour, 7.9 parts of ethanol was then added, and the resultant mixture was heated at steam 'bath temperature for minutes. Approximately parts of water was then added, and the lower layer of the resultant mixture was collected and distilled. There was thus obtained 2,3-bis- (perfluoropropyl)quinoxaline as a clear, colorless liquid boiling at 75 C. under a pressure corresponding to 3 mm. of mercury; 11 1.4195. The nuclear magnetic resonance spectrum showed a C F grouping and aromatic hydrogen. The ultraviolet spectrum showed absorption at 3200 and 2425A.

Analysis.-Calcd. for C14H4F14N3I'F, 57.0%. Found: F, 57.1%.

Found Example X A still pot was charged with 100 parts of the acyloin 5H tetradecafluoro-5-hydroxy-4-octanonesee Example VI--2l0 parts of acetic acid, and 66 parts of bismuth triacetate. The pot was connected to a spinning band distillation column of the type described in U.S. Patent 2,712,-

520, and distillation was begun. About 60 parts of product boiling in the range -115 C. at atmospheric pressure was collected. Upon redistillation there was obtained 30 parts of a yellow liquid boiling at 96 C. at atmospheric pressure which, by gas chromatography, was shown to be an azeotrope of acetic acid and perfluoro-4,5- octanedione-see Example IX. The pure perfluoro-4,5- octanedione was recovered from the azeotrope by shaking with water and distilling the resultant perfluoro4,5-octanedione hydrate from phosphorus pentoxide.

Continued distillation of the original distillation residue afforded 20 parts of a mixture of acetic acid and 3H- tridecafluoro-4,5-octanedione as a yellow liquid boiling at 108-l10 C. at atmospheric pressure. Gas chromatography aflorded the pure 3H-tridecafiuoro-4,5-octanedione as indicated by nuclear magnetic resonance analysis.

The identity of the BH-tridecafiuorot,S-octanedione mm. of mercury to obtain the pure 2-perfluoropropyl-3- (lH-hexafluoropropyl)quinoxaline as plates melting at 42-43 C.v

Analysis-Calcd. for C H N F C, 37.5%; H, 1.1%; F, 55.1%. Found: C, 37.8%; H, 1.5%; F, 55.0%.

Example XI A mixture of 14 parts of the acyloin 1H,6H,10H- hexadecafluoro 6 hydroxy-S-decanone-see Example V11I-8 parts of bismuth triacetate, and 52.5 parts of acetic acid was heated to 110 C. and allowed to cool.

Upon distillation of the reaction mixture there was thus obtained 1.9 parts of an 80% /20% mixture of 1H,10H-

decafluoro-5,6-decanedione as a clear, colorless liquid boiling at 56-65 C. under a pressure corresponding to Example XII A mixture of 11.2 parts of the enediol diester tetradecafluoro 4 octene-4,5 diol di(perfiuorobutyrate)-see Example III-405 parts of acetic acid, and 0.2 part of 10% palladium-on-carbon catalyst was shaken in a con-. ventional glass hydrogenation apparatus under 40 lb./sq. in. hydrogen pressure at room temperature for 18 hours. The resulting reaction mixture was vented to the atmosphere, removed from the reactor, filtered, and the filtrate was diluted with 200 parts of water saturated with sodium chloride. The resultant mixture was extracted with about 70 parts of diethyl ether. After removal of the diethyl ether from the ether extract and subsequent purification by distillation, there was obtained 4H,5H-tetradecafluoro 4,5-octanediol as a clear, colorless liquid boiling at 80 C. under a pressure corresponding to 25 mm. of mercury. On standing, the dihydrotetradecafluorooctanediol solidified. Recrystallization from chloroform afforded pure 4H,5H-tetradecafiuoro-4,5-octanediol in 50% yield as a white crystalline solid melting at 7173 C. Fluorine and proton nuclear magnetic resonance were consistent with the dihydrotetradecafiuorooctanediol structure.

Analysis-Calcd. for C H F O F, 66.8%. Found:

' 'vention is also generic to these new perfiuoro-, w-hydroperfluoro-, and w-chloroperfiuorocarbyl acyloin esters and enediol diestters wherein each perfiuoro-, w-hydroperfluoro-, and w-chloroperfluorocarbyl radical is from three through fourteen'carbons, inclusive. The invention is also generic to the perfiuoro-, w-hydroperfiuoro-, and wchloropenfluorocarbyl acyloins of the structure:

H RCOCIJHR a-diketones of the structure:

RCOCOR andfluorinated a-glycOlS of the structure:

OH OH RCHCHR obtainable variously from the acyloin esters and enediol diesters, all as described in further detail in the foreorn g As discussed above, the operating conditions for the reaction between the nickel carbonyl and the perfluoro-, w-

hydroperfiuoro-, and w-chloroperfiuorocarbyl acyl halides are extremely specific. Thus, the reaction can only be effected at temperatures below 40 C. Only nickel carbonyl and no other metal carbonyl can be used. The reaction must be effected in the presence of benzonitrile. Although inert reaction diluents, such as the cyclic and acyclic perfluoro ethers and the like, can be present, the reaction is most simply efiected when only the three necessary ingredients, viz., nickel carbonyl, benzonitrile, and the polyfluo- 'rocarbacyl halide, are present. The relative proportions of these three, necessary ingredients can vary widely. Thus, excesses of either the polyfiuorocarbacyl halide or the nickel carbonyl over the amounts called for by the stoichiometry can be used. In the sense of driving the reaction farthest to the desired polyfluorinated acyloin esters and polyfluorinated enediol diesters, it will generally be preferable to use an excess of the nickel carbonyl. While the relative amounts of these two reactants are substantially not significant to the ultimate course of the reaction since any unreacted quantities of either can be recovered and the reaction rerun, the same is not true of the benzonitrile. Excess quantities of 'benzonitrile based on the nickel carbonyl can be used, for instance, up to 750% by weight, as per Example III. However, under such conditions the conversion to the desired polyfluorinated acyloin esters and polyfluorinated enediol diesters is markedly reduced. Accordingly, for best operating efliciency, the benzonitrile will be present in amounts ranging from about 25 to about 100% by weight based on the nickel carbonyl.

. Any perfluoro-, w-hydroperfluoro-, or w-chloroperfluorocarbacylhalide wherein the radicals pendent on the carbonyl carbon contain from three through fourteen carbons, inclusive, can be used, including those instances where these polyfluorinated radicalsare cyclic, straight,

or branched chain radicals. The halides of the carbacyl halide function can be halogen of atomic number from 17-35, i.e., the polyfiuorinated carbacyl chlorides, and carbacyl bromides can be used. Because of their present preferred commercial position as to availability and cost, the preferred polyfluorinated carbacyl halides will be the carbacyl chlorides. Also because of their current readier availability, the most preferred perfluoro-, w-hydropen fiuoro-, and w-chloroperfiuorocarbacyl halides will be those which are straight chain in nature. As specifically illustrated in detail in the foregoing examples, mixtures of the polyfluorocarbacyl halides can be used, in which case mixtures of products will be obtained, i.e., the polyfluorinated acyloin esters and polyfluorinated enediol diesters in whichthe various polyfluorocarbyl radicals from the polyfiuorocarbacyl halides will appear variously in the same or different molecule. While these mixtures can in general, at least in part, be separated, some of the isomeric structures arising cannot be separated by conventional techniques, e.g., distillation, and, accordingly, normally it will not be preferred to use mixtures of the carbacyl halides.

More specifically, in place of the polyfluorocarbacyl halides used in the foregoing detailed examples, there can also be used in the process of this invention to prepare additional further examples of the products of this invention the following polyfluorocarbacyl halides: perfluorocaproyl chloride, perfiuoropelargonyl bromide, w-hydroperfluorooenanthyl chloride, w-hydroperfluoropelargonyl bromide, w-hydroperfiuorobutyryl bromide, w-chloroperfluorobutyryl chloride, wchloroperfiuorooenanthyl bromide, w-chloropelargonyl bromide, w-chloroperfluorohendccanoyl bromide, w-chloroperfluoropentadecanoyl bromide, and w-hydroperfluoropentadecanoyl chloride.

Using these and other like polyfluoroacyl halides, there can be mentioned as illustrative of the polyfluoroenediol diesters of the present invention the following compounds made by reaction of the respective polyfluorocarbacyl halides with nickel carbonyl in the presence of benzonitrile under the conditions previously described: 1,8-dichlorododecafluoro 4 octe'ne 4,5-di0l di(3-chlorohexafluorobutyrate), perfluoro-9-octadecene-9,10-dio1 di(per-.

fiuorononanoate) 1H, l4H-tetracosafiuoro-7-tetradecene 7,8-diol di(7H-dodecafluoroheptanoate), 1,10-dichloro. hexadecafiuoro-S-decene-S,6-diol di(5 chlorooctafluorovalerate), 1,30dichlorohexapentacontafluoro-1S-triacontene-l5,l6-dio1 di( 15 chlorooctacosafluoropentadecanoate).

' In a similar fashion, the polyfluorinated acyloin esters of this invention can be prepared in the same fashion by reaction of the requisite polyfluorocarbacyl halide with nickel carbonyl'in the presence of benzonitrile: 7H- docosafluoro--oxo-7-dodecy1 perfluorohexanoate, 1H, 10H,l8H-dotriacontafiuoro-9-oxo-10-octadecyl 9H-hexadecafluorononanoate, 8H,1,14-dichlorotetracosafluoro-7- oxo-8-tetradecyl 7-chlorododecafluoroheptanoate, 1H, 16H,3OH-hexapentacontafiuoro-l5-oxo-16-triacontyl 15H- octacosafluoropentadecanoate, 1H,5H,8H-dodecafluoro-4- oxo-S-octyl 4H-hexafluorobutyrate.

As pointed out previously, these new polyfluorinatcd acyloin esters and polyfluorinated enediol diesters are quite versatile chemical intermediates. They can be readily converted to the related polyfluorinated acyloins, polyfluor-inateddiketones, and polyfluorinated a-glycols. More specifically, the polyfluorinated acyloin esters and polyfluorinated enediol diesters can be converted to the polyfluorinatecl acyloins by simple and direct alcoholysis, which removes, respectively, the polyfluorocarbyl ester group of the aoyloin'esters and both of the polyfluorocarbyl ester groups of the enediol diesters. The reaction is straightforward and simple. The polyfluorinated acyloin or polyfluorinated, enediol diester 'is simply brought in contact with an alcohol, e.g., methanol, al though higher chain alcohols such as ethanol, butyl alco hol, and the like can be used. The reactioninixture is stirred, and generally after a short induction period, an exothermic reaction occurs. Reaction times can vary from as short as fifteen minutes to several hours. The reaction need not be, but can be if desired, externally heated to accomplish the alcoholysis even faster. Examples of the new polyfiuorinated acyloins of the present invention, in addition to those already illustrated in detail, include the following obtainable from the previously illustrated polyfluorinated acyloin esters and polyfluorinated enediol diesters: 7H-d0cosafluoro 7 hydroxy--dodecanone, 1H, 12H,22H tetracontailuoro 12 hydroxy11-docosanone, 1,10-dichlorohexadecafiuoro-6-hydroxy-5-decanone, 16H- hexapentacontafiuorm16-hydroxy-l5-triacontanone.

These polyfiuorinated acyloins can be oxidized directly to the polyfluorosubstituted 1,2-diketones. Suitable oxidation techniques involve bismuth triacetate, for example, at temperatures from 50150 C. or higher. Other conventional organic oxidizing agents, or, for that matter, oxygen itself either alone or in the presence of oxidation catalysts, at ambient or elevated temperatures can serve to effect the oxidation. These same polyfluorin-ated 1,2-diketones can also be prepared directly from the previously illustrated perfiuorosubstituted enediol diesters bysimple pyrolysisfl Generally the pyrolysis will be carried out attemperatures in the range 400700 C. or thereabouts, using conventional pyrolysis equipment, preferably with the normal type packings in the pyrolysis tube. Suitable specific examples of these new polyfluorinated 1,2-diketones include: perfluoro-6,7-dodecanedi one, 1H,22H-tetracontafiuoro-11,12-docosanedione, 1,10- dichlorohexadecafiuoro-S,G-decanedione, 1H,30H hexapentacontafluoro-l 5,16-triacontanedione, H heneicosafluoro-6,7-dodecanedione, 1H,10H,22H nonatriacontafluoro- 1 ,1 1,12-docosanedione, 4H,1,10-dichloropentadecafluoro-5,6-decanedione, and 1H,14H,30H-pentapentacontafln orol 5 16-triacontadione.

Finally, the polyfluorinated acyloin esters, the polyfluorinated enediol diesters, or the derived polyfiuorinated acyloins can be reduced to the polyfluorinated 1,2-diglycols, i.e., the a-glycols. Reduction can be carried out by any conventional chemical means and is most simply effected by hydrogen itself. Reaction conditions can vary as known to those skilled in the hydrogenation art. With these polyfluorinated acyloin esters, enediol diesters, and acyloins, reduction to the polyfluorinated a-glyeols can be effected under the mildest of conditions, e.g., room temperature at 40 lb. hydrogen pressure or thereabouts. Generally some kind of inert reaction medium will be used, such as acetic acid. Catalysts may be used to effect the reaction faster under even milder techniques. With some of the longer chain polyfluorinated acyloin esters, polyfluorinated enediol diesters, and polyfiuorinated acyloins, higher temperatures and higher hydrogen pressures will be required, but normally the reduction to the polyfluorinated a-glycols will not require conditions appreciably more stringent than 100 C. at 1000 lb. hydrogen pressure. Suitable additional examples of these new polyfluorinated a-glycols include: 6H,7H,-docosafluoro- 6,7 dodecanediol, 1H,7H,8H,l4H-tetracosafluoro-7,8-tetradecanediol, 1H,11H,12H,22H-tetracontafluoro-11,12-docosanediol, 5H,6H,1,10-dichlorohexadecafluoro 5,6 decanediol, 15H,16H-hexapentacontafluoro 15,16 triacontanediol.

These various polyfluorosubstituted acyloin esters, enediol diesters, 1,2-diketones, and m-glycols have many varied uses. For instance, the polyfluorosubstituted 1,2- diketones are useful as polymerization photoinitiators, i.e., as materials which, when combined with an addition polymerizable, ethylenically unsaturated monomer, will activate the mixture so that, when the mixture is exposed to light, generally of 1800 to 7000 A., the polyfiuorinated 1,2-diketones decompose under the influence of said light to form active free-radicals which initiate the polymeriza tion of the ethylenically unsaturated monomersee, for

instance, U.S. 2,367,660, where a similar polymerization initiation action is described for the corresponding hydrocarbon compound. By virtue of the high content of fluorine-to-carbon links, these polyfiuorosubstituted 1,2- diketones are stabler than their corresponding hydrocarbon compounds and also have greater affinity for, and accordingly a higher utility in, the polymerization under light-induced conditions of the polyfluorosubstituted ethylenicallyunsaturated monomers. In like manner, the polyfiuorosubstituted acyloins serve similarly as photoinitiators for ethylenically unsaturated monomers, again particularly for the polyfiuorosubstituted ethylenic monomere-see, for instance, US. 2,367,661, where a similar initiating activity is described for the corresponding hyd-rocarbyl acyloins.

The polyfiuorosubstituted 1,2-diketones are also useful in an entirely difierent sense in the polymerization field in that they are polymerizable comonomers for the ethylenically saturated oxoor thiocarbonyl-containing addition polymerizable monomers. More specifically, the

perfluoro-4,5-octanedione of Example IX can be copolymerized with thiocarbonyl difiuoride to form an elastomeric copolymer containing twocombined mole percent of the perfluoro-4,5-octanedione and 98 combined mole percent of the fiuorothiocarbonyl difiuoride. The copolymer is somewhat nervier ,than'the thiocarbonyl difiuoride homopolymer. a g

The polyfluorinated 1,2: .or 'd-glycols have obvious utility as intermediates in the formation of polyfluorosubstituted condensation polyesters.

The enediol diesters by virtue of their diester functionality can, like the oz-glyCOlS, serve as intermediates in the formation of polyfiuorosubstituted condensation polyesters by the well-known technique of ester interchange. Thus, the polyfluorosubstituted enediol diester is mixed with a dibasic acid which is higher boiling than the polyfluorosubstituted carbacyl acid corresponding to the polyfiuorosubstituted carbacyl ester group in the enediol diester structure, and on heating, preferably in the presence of an ester interchange catalyst, the polyfluorosubstituted carbacyl acid moiety of the enediol diester is distilled off and there remains a condensation polyester of the higher boiling dibasic acid and the enediol.

The longer chain acyloins, 1,2-diketones, and a-glycols, and to a lesser extent the acyloins and enediol diesters, are also useful as surfactants, i.e., dispersing agents, particularly for waxes, oils, and greases, and especially for the polyfluorinated low molecular weight polymers.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The process which comprises reacting, in the presence of liquid benzonitrile and at a temperature below 40 C., nickel carbonyl and at least one polyfluoroacyl halide of the formula RCOX wherein R is selected from the group consisting of perfiuoro-, w-hydroperfluoro-, and w-chloroperfluorocarbyl radicals of 3-14 carbons free of aliphatic unsaturation and X is halogen of atomic number 17-35.

2. The process of claim 1 employing a fluorinated valeryl halide.

3. The process of claim 2 employing SH-octafluorovaleryl chloride.

4. The process of claim 1 employing a fluorinated butyryl halide.

5. The process of claim 4 employing perfiuorobutyryl chloride.

6. The process of claim 1 employing a fluorinated glu taryl halide.

' 7. The process of claim 6 employing perfiuoroglutaryl chloride.

8. A compound of the formula i i R -(|1([ -R* c (I wherein R and R are selected from the group consisting of perfluoro-, w-hydroperfluoro-, and w-chloroperfluorocarbyl radicals of 3-14 carbons free of aliphatic unsaturation, and valence a is satisfied by a member of the group consisting of (A) one half of a carbon-to-carbon double bond shared with valence b, an ethylenic linkage between the depicted carbons being formed thereby, in

which case valences c and d are satisfied by and 0 -O( i-R respectively, R and R being chosen from the group consisting of monovalent perfiuoro-, w-hydroperfluoro-, and w-chloroperfluorocarbyl radicals and divalent perfluorocarbyl radicals joined respectively wk and R R and R being of 3-14 carbons free of aliphatic unsaturation and (B) one half of a carbon-to-oxygen double bond,

' the other half of said bond being supplied by valence c,'

in which case valence b is hydrogen, valence d being satisfied by I? 0c-R= R being as defined above.

9. A compound of the formula '0 000a R -C-OHR wherein .R, R and R are as defined in claim 8.

10. A compound of the formula R1-O=C--R? wherein R R R and R are as defined in claim 8.

11. I-I-LIOH hexadecafluoro-S-decene-5,6-diol di(5H- octafiuorovalerate) 12. 5H-tetradecaflnoro-4-oxo-5-octyl perfiuorobu tyrate. 13. Perfiuoro-4-octene-4,5-diol di(perfiuorobutyrate).

References Cited in the file of this patent UNITED STATES PATENTS 2,559,628 Joyce July 10, 1951 2,802,862 Senkbeil Aug. 13, 1957 2,879,298 Seligman Mar. 24, 1959 2,915,531 Wolf et al. Dec. 1, 1959 

1. THE PROCESS WHICH COMPRISES REACTING, IN THE PRESENCE OF LIQUID BENZONITRILE AND AT A TEMPERATURE BELOW 40*C., NICKEL CARBONYL AND AT LEAST ONE POLYFLUOROACYL HALIDE OF THE FORMULA RCOX WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF PERFLUORO-, W-HYDROPERFLUORO-, AND W-CHLOROPERFLUOROCARBYL RADICALS OF 3-14 CARBONS FREE OF ALIPHATIC UNSATURATION AND X IS HALOGEN OF ATOMIC NUMBER 17-35.
 8. A COMPOUND OF THE FORMULA 